SYNTHESIS AND SOLVOLYSIS OF COVALENT SULFONYLMETHYLPERCHLORATES

Six representatives (Ia-If) of a new class of covalent perchlorates, i.e. alkyl- and arylsulfonyl-methylperchlorates have been prepared from the corresponding α-diazosulfones and perchloric acid in an aprotic solvent. The compounds show a remarkable thermal stability, but are sensitive to shock. Hydrolysis of these perchlorates gives the parent sulfinic acid, formic acid and chloric acid. It is a kinetically general base-catalysed reaction as indicated by rate measurements in buffer solutions, solvent deuterium isotope effects and the absence of CH/CD exchange during solvolysis. The Brønsted coefficient for Ia, the activation parameters and the substituent effect on the rates of hydrolysis are discussed in terms of the proposed mechanism. In the fast product determining steps a redox reaction is involved, in which possibly an α-oxosulfone is intermediate. © 1969.